A new catalytic system for the anaerobic oxidation of benzyl alcohols using a tetrazole-amino-saccharin organocatalyst has been established. In a solvent-free and microwave assisted process comprising aqueous tert-butyl hydroperoxide (TBHP) as oxidant, a variety of benzyl alcohols has been efficiently converted to aldehydes under mild conditions. Most reactions are complete within 30 min and the catalyst exhibits varied functional group compatibility. A catalytic cycle for the oxidation of the alcohols promoted by the tetrazole-amino-saccharin derivative is outlined involving radical species. DFT calculations performed for the oxidation of benzyl alcohol with and without organocatalyst show that the rate limiting step of the whole reaction is the cleavage of the OO bond in TBHP with the subsequent hydrogen abstraction from the alcohol. The tetrazole-amino-saccharin organocatalyst assists the H-abstraction from benzyl alcohol by the bound HO radical. The simplicity, selectivity and softness of reaction conditions of the studied organocatalytic protocol suggest a great potential for extensive use in synthetic chemistry.

建立了使用四唑-氨基糖精有机催化剂厌氧氧化苄醇的新催化体系。在包含叔丁基过氧化氢水溶液（TBHP）作为氧化剂的无溶剂微波辅助工艺中，多种苄醇已在温和条件下有效转化为醛。大多数反应在30分钟内完成，催化剂显示出不同的官能团相容性。概述了由四唑-氨基糖精衍生物促进的醇氧化的催化循环，涉及自由基种类。用或不用有机催化剂对苯甲醇的氧化进行的DFT计算表明，整个反应的限速步骤是O的裂解TBHP中的O键以及随后从醇中提取氢。四唑-氨基糖精有机催化剂通过结合的HO自由基帮助从苯甲醇中吸氢。所研究的有机催化方案的反应条件的简单性，选择性和柔软性表明了其在合成化学中的广泛应用的巨大潜力。